Production of water-repellent textiles



Patented Apr. 25,

PRODUCTION OF WATER-REPELLENT TEXTILES Frank Kerr Signaigo, Kenmore, N.Y., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., acorporation 01' Delaware No Drawing. Application August 22, 1946,

Serial No. 692,384

8 Claims. (01. 117-1355) This invention relates to the production ofimproved, water-repellent textiles or other fibrous materialsy and moreparticularly to novel methods for treating such materials to impartpermanent water-repellent characteristics thereto.

The treatment of textile materials with emulsions of parafiins, waxes,resins, and the like, to render them water-repellent has already beenproposed. However, on subsequent customary laundering, washing orcleaning of the textile with detergents, such as soaps or with solvents,these treating agents are, for the most part, removed and the desiredwater repellency becomes lost. A real need has thus existed for awaterrepellent type of finish or' impregnating agent which is useful intreating textile or fabric materials which advantageously will becapable of permanent retention on the fabric to impart permanentwater-repellency characteristics thereto.

It is among the objects of this invention to overcome the above andother disadvantages characterizing prior attempts to obtain awaterrepellent textile material and to provide a novel type of treatingagent and method of rendering textile materials substantiallypermanent-1y water-repellent. A particular object is to provide apermanent water-repellent finish on fabrics or other textiles which willremain substantially unaffected by the customary laundering or othercleaning treatments to which-the same may be subjected during use. Otherobjects and advantages of the invention will be apparent from theensuing description of my invention.

These objects are accomplishedin this invention which broadlycomprisestreating textiles or similar fibrous materials'with a solubletitaniumcompound and a long chain (containing from the invention:

12 to 20 carbon atoms) fatty acid ester or a poly- [hydric alcohol (saidester. having at least one alcoholic hydroxyl and said polyhydricalcohol being free from other reactive groups) in order to impregnatesaid textile orfibrous materials with the resulting reaction product orinsoluble titanium compound.

In a more specific andipre ferred embodiment, the invention comprisestreating textile materials, such as cotton fabrics, at room orslightlyelevated temperatures, with a combination of a water-solubletitanium salt, such as titanyl sulfate, and a long chain monocarboxylicacid ester of glycerol, such as glycerol monostearate, and thenneutralizing, drying and recovering the resulting. impregnated,water-repellent material.

To a clearer understanding of the invention, the following specificexamples are given. These are merely illustrative and are not to beconstrued as limiting the underlying principles of Example I Khaki-dyedpoplin is rendered water-repellent by first impregnating it withglycerol monostearate by treatment in a hot aqueous dispersion ofglycerol monostearate for about 10 minutes, followed by treating for onehour at room temperature in a 25% aqueous solution of titanyl sulfatesaturated with glycerol monostearate. The treated fabric is then passedthrough a 2% ammonia solution, and washed thoroughly with water, anddried. The finished fabric, after subjection to a laundering test,exhibits high water-repellency characteristics upon being subjected to astandard spray test, in compartson with a treated control. Controlstreated with glycerol monostearate alone, and glycerol monostearate plussulfuric acid possess no water repellency after laundering. The waterrepellency of the titanium-treated fabric is retained after washing inalcohol or chloroform.

' Example II Cotton twill fabric is rendered water-repellent by treatingfor about 5 minutes in a saturated acetone solution of glycerolmonostearate, followed after drying by treatment at room temperature forabout 30 minutes, in a 17% solution of titanylsulfate'saturated' withglycerol monostearate. The treated fabric is then thoroughly washed incold water to remove excess titanyl sulfate and free sulfuric acid. Thefinished material possesses excellent water-repellent properties afterlaundering'with soap and warm water. 1 i

Example III Example IV Example III is duplicated, except that a cottonfabric is treated with 12% aqueous solution of titanyl sulfate saturatedwith the monolauryl ether of glycerol. The treated fabric is found toexhibit substantially similar, improved waterrepellent properties.

As already stated, the foregoing examples i1lustrate in detail certainaspects of the invention, but it is to be understood that the inventionis not limited thereto. Thus, in lieu of titanyl sulfate, other solubleinorganic or organic compounds or salts of titanium, as well as varyingamounts of these compounds, can be employed herein. For example,titanium tetrachloride, titanium bromide, titanium sulfate, titaniumnitrate, titanium potassium oxalate, and titanium acetate or lactate,etc., can be used. The TiOz concentration of such solutions can rangefrom about 1% to 30%, but preferably ranges from 15-25%.

Although preferably glycerol monostearate is used in combination with asoluble titanium compound to form upon or impregnate a fabric withwater-repellent finish, other long chain fatty acid esters of apolyhydric alcohol in which the ester contains at least one alcoholichydroxyl and the polyhydric alcohol is free from other reactive groupscan be employed. Long-chain (containing from 12-20 carbon atoms)monocarboxylic acid esters of glycerol, such as glycerol monostearate orlaurate, are especially useful, as are products resulting from theesterification of glycerol with other acids, such as those of myristic,palmitic, stearic, oleic, etc. Again, while the glycerol estersmentioned are preferred for use herein, those obtained from theesterification of other polyhydric alcohols which are free from reactivegroups other than the alcoholic hydroxyl groups, such as from ethyleneglycol, propylene glycol, pentaerythritol and serbitol, etc., can alsobe utilized.

Similarly, while especially useful for applying a water-repellent finishto a textile article, such as cotton fabric, the invention can also beapplied to other woven materials, including those made of wool, rayon,nylon, etc., or to unwoven fibers, threads or filaments, to coat orimpregnate the same. The term textile, here and in the claims, isgeneric to all such materials.

The process of coating the fabrics with the contemplated water-repellentagents is preferably carried out at temperatures ranging from about 25C. to 50 C., and generally may range from 15-100 C., the higher order oftemperature advantageously increasing the rate of processing of thefabrics.

As solvents for the preparation of solutions of titanium salts andglycerol esters. water, acetone. alcohol, or other solvent systemsdetermined by the solubility characteristics of the titanium salts andthe long-chain organic compounds can be employed.

As noted in the examples, after titanatlon the textile is passed throughan ammoniacal solution to effect neutralization thereof and removeexcess residual acid and avoid tendering of the fabric. Such residualacid removal can be effected by extended washing treatment in water orby resorting to other neutralizing agents, such as alkali metalhydroxides or carbonates generally, including potassium or sodiumhydroxide or carbonate, ammonium hydroxide, or related materials.

I claim as my invention:

1. A water-repellent textile containing the reaction product of asoluble titanium compound with a long-chain fatty acid ester of amonomeric polyhydric alcohol, said ester containing at least 1 alcoholichydroxyl and its long-chain fatty acid component having from 12 to 20carbon atoms.

2. A wateflrepellent textile containing the reaction product of awater-soluble titanium salt with a long-chain monocarboxylic acid esterof glycerol, said long-chain fatty acid component containing from 12 to20 carbon atoms.

3. A water-repellent textile containing the reaction product of titanylsulfate with glycerol monostearate.

4. A water-repellent textile containing the reaction product of titanylsulfate with glycerol monolaurate.

5. A method for rendering a textile material water-repellent whichcomprises treating said material with solutions of a soluble titaniumcompound and a long-chain fatty acid ester of a monomeric polyhydricalcohol, said ester containing at least 1 alcoholic hydroxyl and thelong-chain fatty acid component thereof having from 12 to 20 carbonatoms, and then neutralizing, drying and recovering the resultingwater-repellent textile.

6. A method for rendering a textile material Water-repellent whichcomprises treating said material at temperatures ranging from 15 C. toC. with a combination of a water-soluble titanium salt and a long-chainmonocarboxylic acid ester of glycerol, said long-chain componentcontaining from 12 to 20 carbon atoms, and then neutralizing, washing,drying and recovering the resulting Water-repellent textile.

'7. A method for rendering a textile fabric water-repellent whichcomprises treating said fabric at substantially room temperature with acombination of a solution of titanyl sulfate and glycerol monostearate,and then neutralizing, washing and drying the resulting water-repellentfabric.

8. A method for rendering a textile fabric water-repellent whichcomprises treating said fabric at substantially room temperature with acombination of a solution of titanyl sulfate and glycerol monolaurate,and then neutralizing. washing and drying the resulting water-repellentfabric.

FRANK KERR SIGNAIGO.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,035,483 Kirk et a1 Mar. 31,1936 2,035,504 Parkinson et al Mar. 31, 1936 2,356,161 Iler Aug. 22,1944 2,402,857 VanMater June 25, 1946 FOREIGN PATENTS Number CountryDate 391,772 Great Britain July 14, 1932

1. A WATER-REPELLANT TEXTILE CONTAINING THE REACTION PRODUCT OF ASOLUBLE TITANIUM COMPOUND WITH A LONG-CHAIN FATTY ACID ESTER OF AMONOMERIC POLYHYDRIC ALCOHOL, SAID ESTER CONTAINING AT LEAST 1 ALCOHOLICHYDROXYL AND ITS LONG-CHAIN FATTY ACID COMPONENT HAVING FROM 12 TO 20CARBON ATOMS.